Process for producing cycloolefin addition polymer, catalyst for addition polymerization of cycloolefin, and transition metal compound

Abstract

A process for producing a cycloolefin addition polymer comprising addition-polymerizing a cycloolefin in the presence of a catalyst comprising a combination of a specific transition metal compound of Group 4 of the Periodic Table, with an organoaluminum oxy compound, and/or a compound capable of reacting with the Group 4 transition metal compound to form an ion pair. The specific group 4 transition metal compound preferably has a structure such that the group 4 transition metal is bonded to a cyclopentadienyl ring in an η 1 mode. The above-mentioned catalyst exhibits high activity for both of addition homopolymerization of a cycloolefin and addition copolymerization of a cycloolefin with an α-olefin.

1. A process for producing a cycloolefin addition polymer comprising addition-polymerizing a cycloolefin in the presence of a catalyst comprising a combination of (A) a transition metal compound of Group 4 of the Periodic Table, represented by the following general formula (1), with (B) an organoaluminum oxy compound, and/or (C) a compound capable of reacting with the Group 4 transition metal compound (A) to form an ion pair, 
       
         
           
           
               
               
           
         
       
       wherein M represents a transition metal atom of Group 4 of the Periodic Table; R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12  aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; C 5 H 4-x Q x  refers to a cyclopentadienyl ring having “x” number of substituents Q, where x is an integer of 1 to 4, and each Q independently represents a C 1 -C 20  hydrocarbon group which may have a halogen atom or atoms as a substituent, or a silyl group which may have a C 1 -C 12  hydrocarbon group or groups as a substituent; wherein two adjacent Qs in the C 5 H 4-x Q x  may be bonded, together with the carbon atoms to which the two Qs are attached, to form a cyclic moiety having 4 to 20 carbon atoms whereby the C 5 H 4-x Q x  is rendered a polycyclic cyclopentadienyl ring; L is a neutral Lewis base, and y is an integer of 1 or 2. 
     
     
       2. The process for producing a cycloolefin addition polymer according to  claim 1 , wherein, in the general formula (1), the C 5 H 4-x Q x  is bonded to M in an η 1  mode. 
     
     
       3. The process for producing a cycloolefin addition polymer according to  claim 1 , wherein, in the general formula (1), the C 5 H 4-x Q x  is a fluorenyl group or a substituted fluorenyl group. 
     
     
       4. The process for producing a cycloolefin addition polymer according to  claim 1 , wherein the Group 4 transition metal compound (A) is represented by the following general formula (3): 
       
         
           
           
               
               
           
         
       
       wherein M represents a transition metal atom of Group 4 of the Periodic Table; R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12  aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; R 6  to R 9  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom, or a C 1 -C 12  hydrocarbon group which may have a halogen atom or atoms as a substituent, or a silyl group which may have a C 1 -C 12  hydrocarbon group or groups as a substituent; R 6  and R 7 , and R 8  and R 9  may be bonded together to form a ring; and L is a neutral Lewis base. 
     
     
       5. A catalyst for addition-polymerization of a cycloolefin comprising a combination of (A) a transition metal compound of Group 4 of the Periodic Table, represented by the following general formula (1), with (B) an organoaluminum oxy compound, and/or (C) a compound capable of reacting with the Group 4 transition metal compound (A) to form an ion pair, 
       
         
           
           
               
               
           
         
       
       wherein M represents a transition metal atom of Group 4 of the Periodic Table; R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12 , aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; C 5 H 4-x Q x  refers to a cyclopentadienyl ring having “x” number of substituents Q, where x is an integer of 1 to 4, and each Q independently represents a C 1 -C 20  hydrocarbon group which may have a halogen atom or atoms as a substituted, or a silyl group which may have a C 1 -C 12  hydrocarbon group or groups as a substituent; wherein two adjacent Qs in the C 5 H 4-x Q x  may be bonded, together with the carbon atoms to which the two Qs are attached, to form a cyclic moiety having 4 to 20 carbon atoms whereby the C 5 H 4-x Q x  is rendered a polycyclic cyclopentadienyl ring; L is a neutral Lewis base, and y is an integer of 1 or 2. 
     
     
       6. The catalyst for addition-polymerization of a cycloolefin according to  claim 5 , wherein, in the general formula (1), the C 5 H 4-x Q x  is bonded to M in an η 1  mode. 
     
     
       7. The catalyst for addition-polymerization of a cycloolefin according to  claim 5 , wherein, in the general formula (1), the C 5 H 4-x Q x  is a fluorenyl group or a substituted fluorenyl group. 
     
     
       8. The catalyst for addition-polymerization of a cycloolefin according to  claim 5 , wherein the Group 4 transition metal compound (A) is represented by the following general formula (3): 
       
         
           
           
               
               
           
         
       
       wherein M represents a transition metal atom of Group 4 of the Periodic Table; R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12  aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; R 6  to R 9  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom, or a C 1 -C 12  hydrocarbon group which may have a halogen atom or atoms as a substituted, or a silyl group which may have a C 1 -C 12  hydrocarbon group or groups as a substituent; R 9  and R 7 , and R 5  and R 9  may be bonded together to form a ring; and L is a neutral Lewis base. 
     
     
       9. The catalyst for addition-polymerization of a cycloolefin according to  claim 5 , wherein the Group 4 transition metal compound (A) is a titanium compound represented by the following general formula (2): 
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12  aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; and L is a neutral Lewis base. 
     
     
       10. A transition metal compound of Group 4 of the Periodic Table, represented by the following general formula (3): 
       
         
           
           
               
               
           
         
       
       wherein M represents a transition metal atom of Group 4 of the Periodic Table; R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12  aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; R 6  to R 9  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom, or a C 1 -C 12  hydrocarbon group which may have a halogen atom or atoms as a substituted, or a silyl group which may have a C 1 -C 12  hydrocarbon group or groups as a substituent, provided that, in the case when M is titanium, R 6  and R 7 , and/or R 8  and R 9  may be bonded together to form a ring; and L is a neutral Lewis base. 
     
     
       11. The Group 4 transition metal compound according to  claim 10 , which is a titanium compound represented by the following general formula (2): 
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 3  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group or a C 6 -C 12  aryl group; R 4  and R 5  each independently represent a hydrogen atom, a C 1 -C 12  alkyl group, a C 5 -C 12  cycloalkyl group, a C 6 -C 12  aryl group or a halogen atom; and L is a neutral Lewis base.